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Magic Angle Spinning (magic + angle_spinning)
Kinds of Magic Angle Spinning Selected AbstractsNMR spectroscopy of citrate in solids: cross-polarization kinetics in weakly coupled systemsMAGNETIC RESONANCE IN CHEMISTRY, Issue 5 2008Jian Feng Abstract Solid-state NMR spectroscopy is a potentially powerful method for obtaining molecular level structural information crucial for understanding the specific relationship between calcite crystals and occluded organic molecules that are important in biomineralization and biomimetic materials. In this work, a method is developed based on cross-polarization/magic angle spinning (CP/MAS) NMR to measure the heteronuclear distances and obtain structural information for large intracrystalline citrate defects in a synthetic calcite/citrate composite. Using compounds with well-characterized crystal structures, Mg(II) citrate and Sr(II) citrate, a correlation is established between TIS, the CP time, and M2IS, the van Vleck heteronuclear dipolar second moment, which contains distance and structural information. This correlation is supported by peak assignments obtained from calculations of the 13C chemical shifts for crystalline Mg(II) citrate. On the basis of TIS,1versusM2IS correlation, measurement of TIS for carbonate ions associated with citrate defects in a calcite(13C-enriched)/citrate coprecipitate yields an estimate for the distance between citrate and the nearest carbonate carbon that indicates close spatial proximity and provides useful constraints for future computational study. The applicability of TIS,1versusM2IS correlations to other weakly coupled spin-1/2 systems is discussed in terms of the effects of 1H homonuclear dipolar coupling, using the CP kinetics of Zn(II) dihydroxybenzoate and kaolinite for comparison. The results suggest a limited range of correlation constants and indicate that quantitative information can be obtained from CP/MAS kinetics obtained under similar experimental conditions. Copyright © 2008 John Wiley & Sons, Ltd. [source] TROSY effects in MAS solid-state NMRCONCEPTS IN MAGNETIC RESONANCE, Issue 2 2008Veniamin Chevelkov Abstract Use of transverse relaxation-optimized spectroscopy (TROSY) type techniques had a dramatic impact on the study of large proteins with a molecular weight >30kDa for solution-state NMR. In the solid-state, such an effect would not be expected a prior, as the investigated molecules are immobilized. However, local motions induce fluctuations of the local fields experienced by the nuclear spins and, this way, are effective for relaxation. We demonstrate that protein dynamics can significantly influence the resonance line width in ultra high resolution MAS (magic angle spinning) solid-state NMR experiments. Averaging of the 15NH,/, multiplet components as a consequence of 1H decoupling induces effective broadening of the 15N resonance. Application of TROSY type techniques that select only the narrow component of the multiplet pattern results in an increased resolution and, thus, will be of benefit for MAS solid-state NMR spectroscopy. © 2008 Wiley Periodicals, Inc. Concepts Magn Reson Part A 32A: 143,156, 2008. [source] Setting up 13C CP/MAS experimentsCONCEPTS IN MAGNETIC RESONANCE, Issue 1 2004R.E. Taylor Abstract The 13C cross-polarization (CP) technique combined with magic angle spinning (MAS) has become one of the more commonly performed solid-state nuclear magnetic resonance (NMR) experiments. The basics of initially setting up the experiment are given and used to illustrate such NMR phenomena as rotational echoes, homogeneous and inhomogeneous interactions, continuous wave 1H decoupling, and coupling of quadrupolar 14N nuclei to 13C nuclei. The polarization transfer from the protons to the carbons is described briefly with the usual thermodynamic and quantum mechanical models. The setup and use of the experiment for routine analyses are discussed. © 2004 Wiley Periodicals, Inc. Concepts Magn Reson 22A: 37,49, 2004. [source] Characterization of biochar from fast pyrolysis and gasification systemsENVIRONMENTAL PROGRESS & SUSTAINABLE ENERGY, Issue 3 2009Catherine E. Brewer Abstract Thermochemical processing of biomass produces a solid product containing char (mostly carbon) and ash. This char can be combusted for heat and power, gasified, activated for adsorption applications, or applied to soils as a soil amendment and carbon sequestration agent. The most advantageous use of a given char depends on its physical and chemical characteristics, although the relationship of char properties to these applications is not well understood. Chars from fast pyrolysis and gasification of switchgrass and corn stover were characterized by proximate analysis, CHNS elemental analysis, Brunauer-Emmet-Teller (BET) surface area, particle density, higher heating value (HHV), scanning electron microscopy, X-ray fluorescence ash content analysis, Fourier transform infrared spectroscopy using a photo-acoustic detector (FTIR-PAS), and quantitative 13C nuclear magnetic resonance spectroscopy (NMR) using direct polarization and magic angle spinning. Chars from the same feedstocks produced under slow pyrolysis conditions, and a commercial hardwood charcoal, were also characterized. Switchgrass and corn stover chars were found to have high ash content (32,55 wt %), much of which was silica. BET surface areas were low (7,50 m2/g) and HHVs ranged from 13 to 21 kJ/kg. The aromaticities from NMR, ranging between 81 and 94%, appeared to increase with reaction time. A pronounced decrease in aromatic CH functionality between slow pyrolysis and gasification chars was observed in NMR and FTIR-PAS spectra. NMR estimates of fused aromatic ring cluster size showed fast and slow pyrolysis chars to be similar (,7,8 rings per cluster), while higher-temperature gasification char was much more condensed (,17 rings per cluster). © 2009 American Institute of Chemical Engineers Environ Prog, 2009 [source] UV-vis-Induced Vitrification of a Molecular Crystal,ADVANCED FUNCTIONAL MATERIALS, Issue 10 2007T. Naito Abstract A charge-transfer complex of 2,5-dimethyl- N,N,-dicyanoquinonediimine (DM) with silver (crystalline Ag(DM)2, defined as ,) is irreversibly transformed by UV-vis illumination. Depending on the illumination conditions, three new types of solids (defined as ,, ,, and ,) with different structural and physical properties are obtained and examined by a variety of analytical techniques, including solid-state, high-resolution, cross-polarization magic angle spinning (CP-MAS) 13C,NMR, elemental analysis (EA), mass spectrometry (MS), X-ray absorption fine structure (XAFS), and powder X-ray diffraction (XRD). The CP-MAS, EA, MS, and XAFS results indicate that compound , is a glass state of Ag(DM)2. The transformation from crystalline (,) to amorphous (,) solid Ag(DM)2 is an irreversible exothermic glass transition (glass-transition temperature 155.2,°C; ,H,=,,126.8,kJ,mol,1), which implies that the glass form is thermodynamically more stable than the crystalline form. Compound , (Ag(DM)1.5) consists of silver nanoparticles (diameter (7,±,2),nm ) dispersed in a glassy matrix of neutral DM molecules. The N,CN,Ag coordination bonds of the , form are not maintained in the , form. Decomposition of , by intense illumination results in a white solid (,), identified as being composed of silver nanoparticles (diameter (60,±,10),nm). Physical and spectroscopic (XAFS) measurements, together with XRD analysis, indicate that the silver nanoparticles in both , and , are crystalline with lattice parameters similar to bulk silver; however, the magnetic susceptibilities differ from bulk silver. [source] 1H magnetic resonance spectroscopy of preinvasive and invasive cervical cancer: In vivo,ex vivo profiles and effect of tumor loadJOURNAL OF MAGNETIC RESONANCE IMAGING, Issue 3 2004Marrita M. Mahon PhD Abstract Purpose To compare in vivo 1H magnetic resonance (MR) spectra of preinvasive and invasive cervical lesions with ex vivo magic angle spinning (MAS) spectra of intact biopsies from the same subjects and to establish the effects of tumor load in the tissue sampled on the findings. Materials and Methods A total of 51 subjects (nine with normal cervix, 10 with cervical intraepithelial neoplasia [CIN], and 32 with cervical cancer) underwent endovaginal MR at 1.5 T. Single-voxel (3.4 cm3) 1H MR spectra were acquired and voxel tumor load was calculated (tumor volume within voxel as a percentage of voxel volume). Resonances from triglycerides ,CH2 and ,CH3 and choline-containing compounds (Cho) were correlated with voxel tumor load. Biopsies analyzed by 1H MAS-MR spectroscopy (MRS) had metabolite levels correlated with tumor load in the sample at histology. Results In vivo studies detected Cho in normal, CIN, and cancer patients with no significant differences in levels (P = 0.93); levels were independent of voxel tumor load. Triglyceride ,CH2 and ,CH3 signals in-phase with Cho were present in 77% and 29%, respectively, of cancer subjects (but not in normal women or those with CIN), but did not correlate with voxel tumor load. Ex vivo cancer biopsies showed levels of triglycerides ,CH2 and ,CH3 and of Cho that were significantly greater than in normal or CIN biopsies (P < 0.05); levels were independent of the tumor load in the sample. The presence of ,CH2 in vivo predicted the presence of cancer with a sensitivity and specificity of 77.4% and 93.8% respectively, positive (PPV) and negative (NPV) predictive values were 96% and 68.2%; for ,CH2 ex vivo, sensitivity was 100%; specificity, 69%; PPV, 82%; and NPV, 100%. Conclusion Elevated lipid levels are detected by MRS in vivo and ex vivo in cervical cancer and are independent of tumor load in the volume of tissue sampled. J. Magn. Reson. Imaging 2004;19:356,364. © 2004 Wiley-Liss, Inc. [source] A solid-state NMR study of phase structure, molecular interactions, and mobility in blends of citric acid and paracetamolJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 5 2009S. Schantz Abstract Citric acid anhydrate (CAA) and paracetamol (PARA), prepared as crystalline physical mixtures and as amorphous blends, were studied using 13C solid-state cross polarization magic angle spinning (CPMAS) NMR. Amorphous blends showed significant line broadening from the conformational distribution as compared to the crystalline samples. Also, chemical shift variations were observed between crystalline and amorphous blends, which were attributed to differences in intermolecular interactions. Averaging of proton rotating-frame spin-lattice relaxation times (T1,) probed via different 13C sites in the amorphous blends confirmed molecular level mixing. For some, initially amorphous, sample compositions the onset of crystallization was evident directly from spectra and from the significantly longer T1, relaxations. Thus, crystallization caused phase separation with properties of the two phases resembling those of pure CAA and PARA, respectively. 13C spectra of amorphous 50/50 (w/w, %) CAA/PARA recorded from above the glass transition temperature broadened as the temperature increased to a maximum at T,,,Tg,+,33 K. This was the result of a dynamic interference between the line narrowing techniques being applied and the time scale of molecular reorientation in the miscible melt. The derived average correlation time was found to correspond well with previous results from melt rheology. We conclude that the underlying reasons for physical instability (i.e., crystallization from the miscible melt, including molecular interactions and dynamics) of this class of amorphous binary mixtures can be effectively evaluated using NMR spectroscopy. © 2008 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 98:1862,1870, 2009 [source] HIGH-RESOLUTION MAGIC ANGLE SPINNING NMR ANALYSIS OF WHOLE CELLS OF CHAETOCEROS MUELLERI (BACILLARIOPHYCEAE) AND COMPARISON WITH 13C-NMR AND DISTORTIONLESS ENHANCEMENT BY POLARIZATION TRANSFER 13C-NMR ANALYSIS OF LIPOPHILIC EXTRACTS,JOURNAL OF PHYCOLOGY, Issue 3 2004Matilde S. Chauton Lipid composition in extracted samples of Chaetoceros muelleri Lemmermann was studied with 13C-NMR and distortionless enhancement by polarization transfer (DEPT) 13C-NMR, resulting in well-resolved 13C-NMR spectra with characteristic resonance signals from carboxylic, olefinic, glyceryl, methylene, and methyl groups. The application of a DEPT pulse sequence aided in the assignment of methylene and methine groups. Resonance signals were compared with literature references, and signal assignment included important unsaturated fatty acids such as eicosapentaenoic and docosahexaenoic and also phospholipids and glycerols. Results from the extracted samples were used to assign resonance signals in a high-resolution magic angle spinning (HR MAS) DEPT 13C spectrum from whole cells of C. muelleri. The NMR analysis on whole cells yielded equally good information on fatty acids and also revealed signals from carbohydrates and amino acids. Broad resonance signals and peak overlapping can be a problem in whole cell analysis, but we found that application of HR MAS gave a well-resolved spectrum. The chemical shift of metabolites in an NMR spectrum depends on the actual environment of nuclei during analysis, and some differences could therefore be expected between extracted and whole cell samples. The shift differences were small, and assignment from analysis of lipophilic extract could be used to identify peaks in the whole cell spectrum. HR MAS 13C-NMR therefore offers a possibility for broad-range metabolic profiling directly on whole cells, simultaneously detecting metabolites that are otherwise not detected in the same analytical set up and avoiding tedious extraction procedures. [source] Neonatal Alcohol-Induced Region-Dependent Changes in Rat Brain Neurochemistry Measured by High-Resolution Magnetic Resonance SpectroscopyALCOHOLISM, Issue 10 2008Shonagh K. O'Leary-Moore Background:, Maternal drinking during pregnancy can lead to a range of deleterious outcomes in the developing offspring that have been collectively termed fetal alcohol spectrum disorders (FASDs). There is interest and recognized value in using non-invasive neuroimaging techniques such as magnetic resonance imaging (MRI) and magnetic resonance spectroscopy (MRS) to characterize, respectively, structural and biochemical alterations in individuals with FASDs. To date, however, results with MRS have been inconsistent regarding the degree and/or nature of abnormalities. Methods:, High-resolution magic angle spinning (HR-MAS) proton (1H) MRS is an ex vivo neuroimaging technique that can acquire spectra in small punches of intact tissue, providing clinically relevant neurochemical information about discrete brain regions. In this study, HR-MAS 1H MRS was used to examine regional neurochemistry in frontal cortex, striatum, hippocampus, and cerebellum of young rats previously exposed to ethanol as neonates. Key neurochemicals of interest included N-acetyl-aspartate (NAA), glutamate, GABA, glutamine, creatine, choline and myo -inositol. Results:, Daily neonatal alcohol exposure from postnatal day 4 (PN4) through PN9 significantly reduced levels of NAA and taurine in the cerebellum and striatum, and induced sex-dependent reductions in cerebellar glutamate when measured on PN16. In addition, myo -inositol was significantly increased in cerebellum. The frontal cortex and hippocampus were virtually unaffected by this neonatal alcohol exposure. Conclusion:, Results of this research may have implications for understanding the underlying neurobiology associated with FASDs and aid in testing treatments in the future. Ongoing studies are assessing the developmental persistence of and/or maturational recovery from these changes. [source] Natural Abundance 43Ca NMR Spectroscopy of Tobermorite and Jennite: Model Compounds for C,S,HJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 2 2009Geoffrey M. Bowers There are few effective methods for characterizing the molecular scale structural environments of Ca2+ in hydrated cements, which has limited our ability to understand the structure of, for example, Ca,silicate hydrate (C,S,H). 43Ca nuclear magnetic resonance (NMR) spectroscopy has long been considered too insensitive to provide useful data in this regard, but 43Ca magic angle spinning (MAS) NMR spectra reported here for synthetic tobermorite and jennite with naturally abundant levels of 43Ca demonstrate that this is a viable approach. We show that spectra with useful signal/noise ratios can be obtained in a reasonable acquisition period (,2 days) using an H0 field strength of 21.1 T, 5 mm rotors spinning at a frequency of 5 kHz, and a double frequency sweep preparatory pulse sequence. Tobermorite and jennite produce relatively broad resonances due to their complex structures and structural disorder, however, the chemical shift differences between six-coordinate 43Ca in jennite and seven-coordinate 43Ca in 11 Å tobermorite are large enough that the signals are entirely resolved at this field. These data suggest that signal from ideal tobermorite-like and jennite-like sites in cement C,S,H can most likely be distinguished by 43Ca NMR and that this method will be a powerful approach for studying cement-based ceramic materials in the coming decade. [source] Preparation of Scratch- and Abrasion-Resistant Polymeric Nanocomposites by Monomer Grafting onto Nanoparticles, 4,MACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 3 2003Frank Bauer Abstract To obtain transparent, scratch- and abrasion-resistant coating materials a high content of nanosized silica and alumina filler was embedded in radiation-curable acrylate formulations by acid catalyzed silylation using trialkoxysilanes. 29Si magic angle spinning (MAS) NMR spectroscopy and matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF MS) were used to elucidate the structure of the surface-grafted methacryloxypropyl-, vinyl-, and n -propyltrimethoxysilane. 29Si MAS NMR measurements revealed a predominance of T2 and T3 structures of silicon atoms, i.e., silane oligomers have been formed by an extensive loss of water. For methacryloxypropyltrimethoxysilane, the proportion of the highly condensed T3 silicon atoms was estimated to be 75%. In accordance with these NMR findings, MALDI-TOF MS showed highly condensed oligomeric siloxanes of more than 20 monomeric silane units. The degree of silane condensation is higher on alumina than on silica, irrespective to the addition of maleic acid as catalyst. Moreover, completely condensed silsesquioxanes, e.g., octamers, decamers, and dodecamers, were detected. Based on the observed MS pattern, a ladder-like arrangement of two linked siloxane chains forming connected eight-membered rings is proposed, which is similar for all of the condensed organosilanes under study. The grafted polysiloxanes lead to an organophilation of inorganic nanofillers and improve their dispersibility in acrylate suspensions. Proposed ladder-like arrangement of the T3 structure of silicon atoms in polysiloxanes grafted on the silica surface. [source] 1H-HRMAS NMR study of smoked Atlantic salmon (Salmo salar)MAGNETIC RESONANCE IN CHEMISTRY, Issue 9 2010David Castejón Abstract High-resolution magic angle spinning (HRMAS) NMR spectroscopic data of smoked Atlantic salmon (Salmo salar) were fully assigned by combination of one- and two-dimensional-HRMAS experiments. Complete representative spectra, obtained after few minutes of analysis time, revealed a large number of minor and major compounds in the sample. The methodology is limited by the low sensitivity of NMR, and therefore HRMAS only enables the determination of the most relevant components. These were fatty acids (FAs), carbohydrates, nucleoside derivatives, osmolytes, amino acids, dipeptides and organic acids. For the first time, spectra were resolved sufficiently to allow semiquantitative determination in intact muscle of the highly polyunsaturated FA 22:6 ,-3. Additionally, the feasibility of 1H-HRMAS NMR metabolite profiling was tested to identify some bioactive compounds during storage. This profiling was carried out by the non-destructive and direct analysis (i.e. without requiring sample preparation and multiple step procedures) of intact salmon muscle. The proposed procedure can be applied to a large number of samples with high throughput due to the short time of analysis and quick evaluation of the data. Copyright © 2010 John Wiley & Sons, Ltd. [source] Efficient low-power heteronuclear decoupling in 13C high-resolution solid-state NMR under fast magic angle spinningMAGNETIC RESONANCE IN CHEMISTRY, Issue S1 2007Mrignayani Kotecha Abstract The use of a low-power two-pulse phase modulation (TPPM) sequence is proposed for efficient 1H radio frequency (rf) decoupling in high-resolution 13C solid-state NMR (SSNMR) under fast MAS conditions. Decoupling efficiency for different low-power decoupling sequences such as continuous-wave (cw), TPPM, XiX, and ,-pulse (PIPS) train decoupling has been investigated at a spinning speed of 40 kHz for 13C CPMAS spectra of uniformly 13C - and 15N -labeled L -alanine. It was found that the TPPM decoupling sequence, which was originally designed for high-power decoupling, provides the best decoupling efficiency at low power among all the low-power decoupling sequences examined here. Optimum performance of the low-power TPPM sequence was found to be obtained at a decoupling field intensity (,1) of ,,R/4 with a pulse flip angle of ,, and a phase alternation between ± ,(, = ,20° ), where ,R/2, is the spinning speed. The sensitivity obtained for 13CO2,, 13CH, and 13CH3 in L -alanine under low-power TPPM at ,1/2, of 10 kHz was only 5,15% less than that under high-power TPPM at ,1/2, of 200 kHz, despite the fact that only 0.25% of the rf power was required in low-power TPPM. Analysis of the 13CH2 signals for uniformly 13C- and 15N-labeled L -isoleucine under various low-power decoupling sequences also confirmed superior performance of the low-power TPPM sequence, although the intensity obtained by low-power TPPM was 61% of that obtained by high-power TPPM. 13C CPMAS spectra of 13C -labeled ubiquitin micro crystals obtained by low-power TPPM demonstrates that the low-power TPPM sequence is a practical option that provides excellent resolution and sensitivity in 13C SSNMR for hydrated proteins. Copyright © 2007 John Wiley & Sons, Ltd. [source] Environmentally friendly flame retardants.MAGNETIC RESONANCE IN CHEMISTRY, Issue S1 2007A detailed solid-state NMR study of melamine orthophosphate Abstract We used solid-state NMR spectroscopy to gain detailed information about the proton positions, proximities and the hydrogen-bonding network in the environmentally friendly flame retardant melamine orthophosphate (MP). High-resolution proton one- and two-dimensional solid-state NMR spectra were obtained at high external magnetic field in combination with fast magic angle spinning of the sample. Furthermore, we recorded homo- and heteronuclear correlation spectra of types 15N15N, 1H13C, 1H15N and 1H31P. In addition, we determined the geometry of the NH and NH2 groups in MP by 15N1H heteronuclear recoupling experiments. We were able to completely assign the different isotropic chemical shifts in MP. Furthermore, we could identify the protonation of the melamine and orthophosphate moieties. The experimental results are discussed in connection with the structural model obtained by powder X-ray diffraction together with a combined molecular modeling-Rietveld refinement approach (De Ridder et al. Helv. Chim. Acta 2004; 87: 1894). We show that the geometry of the NH2 groups can only be successfully estimated by solid-state NMR. Copyright © 2007 John Wiley & Sons, Ltd. [source] 17O NMR in room temperature phase of La2Mo2O9 fast oxide ionic conductorMAGNETIC RESONANCE IN CHEMISTRY, Issue 5 2005Joel Emery Abstract A room temperature 17O NMR study of La2Mo2O9, a fast oxide ionic conductor exhibiting a phase transition at 580 °C between a low-temperature ,-phase and a high-temperature ,-phase, is presented. Four partly overlapping quasi-continuous distributions of oxygen sites are evidenced from 1D magic angle spinning (MAS) and 2D triple quantum MAS NMR experiments. They can be correlated with the three oxygen sites O1, O2 and O3 of the high-temperature crystal structure. The low-temperature phase is characterized by two distributed sites of type O1, which proves that the symmetry is lower than in the cubic high-temperature phase. Two-dimensional experiments show that there is no dynamic exchange process, on the NMR time-scale, between the different oxygen sites at room temperature, which agrees well with conductivity results. Copyright © 2005 John Wiley & Sons, Ltd. [source] Conformation analysis and molecular mobility of ethylene and tetrafluoroethylene copolymer using solid-state 19F MAS and 1H , 19F CP/MAS NMR spectroscopyMAGNETIC RESONANCE IN CHEMISTRY, Issue 7 2004Keitaro Aimi Abstract The changes in the conformation and molecular mobility accompanied by a phase transition in the crystalline domain were analyzed for ethylene (E) and tetrafluoroethylene (TFE) copolymer, ETFE, using variable-temperature (VT) solid-state 19F magic angle spinning (MAS) and 1H , 19F cross-polarization (CP)/MAS NMR spectroscopy. The shifts of the signals for fluorines in TFE units to higher frequency and the continuing decrease and increase in the T1,F values suggest that conformational exchange motions exist in the crystalline domain between 42 and 145 °C. Quantum chemical calculations of magnetic shielding constants showed that the high-frequency shift of TFE units should be induced by trans to gauche conformational changes at the CH2CF2 linkage in the E,TFE unit. Although the 19F signals of the crystalline domain are substantially overlapped with those of the amorphous domain at ambient probe temperature (68 °C), they were successfully distinguished by using the dipolar filter and spin-lock pulse sequences at 145 °C. The dipolar coupling constants for the crystalline domain, which can be estimated by fitting the dipolar oscillation behaviors in the 1H , 19F CP curve, showed a significant decrease with increasing temperature from 42 to 145 °C. This is due to the averaging of 1H19F dipolar interactions originating from the molecular motion in the crystalline domain. The increase in molecular mobility in the crystalline domain was clearly shown by VT T1,F and 1H , 19F CP measurements in the phase transition temperature range. Copyright © 2004 John Wiley & Sons, Ltd. [source] NMR methods for studying the structure and dynamics of oncogenic and antihistaminic peptides in biomembranesMAGNETIC RESONANCE IN CHEMISTRY, Issue 2 2004Christina Sizun Abstract We present several applications of both wide-line and magic angle spinning (MAS) solid-state NMR of bicelles in which are embedded fragments of a tyrosine kinase receptor or enkephalins. The magnetically orientable bicelle membranes are shown to be of particular interest for studying the functional properties of lipids and proteins in a state that is very close to their natural environment. Quadrupolar, dipolar and chemical shielding interactions can be used to determine minute alterations of internal membrane dynamics and the orientation of peptides with respect to the membrane plane. MAS of bicelles can in turn lead to high-resolution proton spectra of hydrated membranes. Using deuterium,proton contrast methods one can then obtain pseudo-high-resolution proton spectra of peptides or proteins embedded in deuterated membranes and determine their atomic 3D structure using quasi-conventional liquid-state NMR methods. Copyright © 2004 John Wiley & Sons, Ltd. [source] 31P CP/MAS NMR of polycrystalline and immobilized phosphines and catalysts with fast sample spinningMAGNETIC RESONANCE IN CHEMISTRY, Issue 6 2003S. Reinhard Abstract Cross-polarization (CP) at fast magic angle spinning (MAS) frequencies leads to a splitting of the Hartmann,Hahn (HH) matching profile into a centerband and additional bands of higher orders. The matching profiles differ with the substance categories. Therefore, signal intensity is usually lost, when e.g. the routine standard NH4H2PO4 is used for optimizing the 1H,31P HH match prior to measuring phosphines and their metal complexes in polycrystalline or immobilized form. Here, a variety of model compounds, such as Ph2PCH2CH2PPh2 and (CO)2Ni(PPh3)2, which can be used as 31P CP standards for analogous substances or materials are presented. Investigating the influences of MAS frequency, contact time, 1H pulse power and sample volume on the matching profiles of the model compounds leads to general trends. Thereby, a new strategy for measuring difficult samples with CP at high MAS rates has been developed: their optimum CP parameters are derived from the most intense maxima in the HH matching profiles of the corresponding model compounds. This new strategy is compared with variations of a conventional ramp sequence. Although the latter generally provide smaller signal half-widths, the new strategy leads to higher signal intensities. The new method was successfully applied to polycrystalline and immobilized phosphines and catalysts. Copyright © 2003 John Wiley & Sons, Ltd. [source] Solid-state 1H , 19F/19F , 1H CP/MAS NMR study of poly(vinylidene fluoride)MAGNETIC RESONANCE IN CHEMISTRY, Issue 2 2002Shinji Ando Abstract Solid-state 1H , 19F and 19F , 1H cross-polarization magic angle spinning (CP/MAS) NMR spectra have been investigated for a semicrystalline fluoropolymer, namely poly(vinylidene fluoride) (PVDF). The 1H , 19F CP/MAS spectra can be fitted by five Lorentzian functions, and the amorphous peaks were selectively observed by the DIVAM CP pulse sequences. Solid-state spin-lock experiments showed significant differences in T1,F and T1,H between the crystalline and amorphous domains, and the effective time constants, THF* and T1,*, which were estimated from the 1H , 19F CP curves, also clarify the difference in the strengths of dipolar interactions. Heteronuclear dipolar oscillation behaviour is observed in both standard CP and 1H , 19F inversion recovery CP (IRCP) experiments. The inverse 19F , 1H CP-MAS and 1H , 19F CP-drain MAS experiments gave complementary information to the standard 1H , 19F CP/MAS spectra in a manner reported in our previous papers for other fluoropolymers. The value of NF/NH (where N is a spin density) estimated from the CP-drain curve is within experimental error equal to unity, which is consistent with the chemical structure. Copyright © 2001 John Wiley & Sons, Ltd. [source] Cerebral activation by fasting induces lactate accumulation in the hypothalamusMAGNETIC RESONANCE IN MEDICINE, Issue 2 2009Inês R. Violante Abstract Carbon-13 (13C) high-resolution magic angle spinning (HR-MAS) spectroscopy was used to investigate the neuroglial coupling mechanisms underlying appetite regulation in the brain of C57BL/6J mice metabolizing [1- 13C]glucose. Control fed or overnight fasted mice received [1- 13C]glucose (20 ,mol/g intraperitoneally [i.p.]), 15 min prior to brain fixation by focused microwaves. The hypothalamic region was dissected from the rest of the brain and 13C HR-MAS spectra were obtained from both biopsies. Fasting resulted in a significant increase in hypothalamic [3- 13C]lactate and [2- 13C],-aminobutyric acid (GABA) relative to the remaining brain. Administration of the orexigenic peptide ghrelin (0.3 nmol/g i.p.) did not increase hypothalamic [3- 13C]lactate or [2- 13C]GABA, suggesting that ghrelin signaling is not sufficient to elicit all the metabolic consequences of hypothalamic activation by fasting. Our results indicate that the hypothalamic regulation of appetite involves, in addition to the well-known neuropeptide signaling, increased neuroglial lactate shuttling and augmented GABA concentrations. Magn Reson Med, 2009. © 2009 Wiley-Liss, Inc. [source] Evaluation of lactate and alanine as metabolic biomarkers of prostate cancer using 1H HR-MAS spectroscopy of biopsy tissuesMAGNETIC RESONANCE IN MEDICINE, Issue 3 2008May-Britt Tessem Abstract The goal of this study was to investigate the use of lactate and alanine as metabolic biomarkers of prostate cancer using 1H high-resolution magic angle spinning (HR-MAS) spectroscopy of snap-frozen transrectal ultrasound (TRUS)-guided prostate biopsy tissues. A long-echo-time rotor-synchronized Carr-Purcell-Meiboom-Gill (CPMG) sequence including an electronic reference to access in vivo concentrations (ERETIC) standard was used to determine the concentrations of lactate and alanine in 82 benign and 16 malignant biopsies (mean 26.5% ± 17.2% of core). Low concentrations of lactate (0.61 ± 0.28 mmol/kg) and alanine (0.14 ± 0.06 mmol/kg) were observed in benign prostate biopsies, and there was no significant difference between benign predominantly glandular (N = 54) and stromal (N = 28) biopsies between patients with (N = 38) and without (N = 44) a positive clinical biopsy. In biopsies containing prostate cancer there was a highly significant (P < 0.0001) increase in lactate (1.59 ± 0.61 mmol/kg) and alanine (0.26 ± 0.07 mmol/kg), and minimal overlap with lactate concentrations in benign biopsies. This study demonstrates for the first time very low concentrations of lactate and alanine in benign prostate biopsy tissues. The significant increase in the concentration of both lactate and alanine in biopsy tissue containing as little as 5% cancer could be exploited in hyperpolarized 13C spectroscopic imaging (SI) studies of prostate cancer patients. Magn Reson Med 60:510,516, 2008. © 2008 Wiley-Liss, Inc. [source] Resolution of creatine and phosphocreatine 1H signals in isolated human skeletal muscle using HR-MAS 1H NMRMAGNETIC RESONANCE IN MEDICINE, Issue 6 2008Jin-Hong Chen Abstract Proton NMR spectra of freshly isolated human skeletal muscle samples contain creatine and phosphocreatine resonances with distinct chemical shifts that are easily visualized with magic angle spinning (MAS, spinning the sample rapidly at 54.7° with respect to the magnetic field) methods. The identification of the phosphocreatine resonance was based on two findings: that (i) the possible small dipolar coupling does not contribute to line splitting under rapid MAS, and (ii) the 1H signal decreases concurrently with the phosphocreatine resonance observed in 31P NMR experiments. In the MAS 1H spectra, the phosphocreatine resonance remains a singlet with a linewidth of less than 3 Hz. The creatine resonances are split into two peaks with linewidths at half height of approximately 2 and 6 Hz, respectively. The resonance with the broader linewidth represents creatine that is significantly motion-restricted and suggests that a creatine pool in muscle tissue is highly compartmentalized. Magn Reson Med 59:1221,1224, 2008. © 2008 Wiley-Liss, Inc. [source] High-resolution magic angle spinning proton NMR analysis of human prostate tissue with slow spinning ratesMAGNETIC RESONANCE IN MEDICINE, Issue 3 2003Jennifer L. Taylor Abstract The development of high-resolution magic angle spinning (HR-MAS) NMR spectroscopy for intact tissue analysis and the correlations between the measured tissue metabolites and disease pathologies have inspired investigations of slow-spinning methodologies to maximize the protection of tissue pathology structures from HR-MAS centrifuging damage. Spinning sidebands produced by slow-rate spinning must be suppressed to prevent their complicating the spectral region of metabolites. Twenty-two human prostatectomy samples were analyzed on a 14.1T spectrometer, with HR-MAS spinning rates of 600 Hz, 700 Hz, and 3.0 kHz, a repetition time of 5 sec, and employing various rotor-synchronized suppression methods, including DANTE, WATERGATE, TOSS, and PASS pulse sequences. Among them, DANTE, as the simplest scheme, has shown the most potential in suppression of tissue water signals and spinning sidebands, as well as in quantifying metabolic concentrations. Magn Reson Med 50:627,632, 2003. © 2003 Wiley-Liss, Inc. [source] High-resolution 1H NMR spectroscopy in rat liver using magic angle turning at a 1 Hz spinning rateMAGNETIC RESONANCE IN MEDICINE, Issue 5 2002Jian Zhi Hu Abstract It is demonstrated that a high-resolution 1H NMR spectrum of excised rat liver can be obtained using the technique of magic angle turning (MAT) at a sample spinning rate of 1 Hz. A variant of the phase-corrected MAT (PHORMAT) pulse sequence that includes a water suppression segment was developed for the investigation. The spectral resolution achieved with PHORMAT approaches that obtained from a standard magic angle spinning (MAS) experiment at a spinning rate of several kHz. With such ultra-slow spinning, tissue and cell damage associated with the standard MAS experiment is minimized or eliminated. The technique is potentially useful for obtaining high-resolution 1H spectra in live animals. Magn Reson Med 47:829,836, 2002. © 2002 Wiley-Liss, Inc. [source] Quantification of metabolites in breast cancer patients with different clinical prognosis using HR MAS MR spectroscopyNMR IN BIOMEDICINE, Issue 4 2010Beathe Sitter Abstract Absolute quantitative measures of breast cancer tissue metabolites can increase our understanding of biological processes. Electronic REference To access In vivo Concentrations (ERETIC) was applied to high resolution magic angle spinning MR spectroscopy (HR MAS MRS) to quantify metabolites in intact breast cancer samples. The ERETIC signal was calibrated using solutions of creatine and TSP. The largest relative errors of the ERETIC method were 8.4%, compared to 4.4% for the HR MAS MRS method using TSP as a standard. The same MR experimental procedure was applied to intact tissue samples from breast cancer patients with clinically defined good (n,=,13) and poor (n,=,16) prognosis. All samples were examined by histopathology for relative content of different tissue types and proliferation index (MIB-1) after MR analysis. The resulting spectra were analyzed by quantification of tissue metabolites (,-glucose, lactate, glycine, myo-inositol, taurine, glycerophosphocholine, phosphocholine, choline and creatine), by peak area ratios and by principal component analysis. We found a trend toward lower concentrations of glycine in patients with good prognosis (1.1,µmol/g) compared to patients with poor prognosis (1.9,µmol/g, p,=,0.067). Tissue metabolite concentrations (except for ,-glucose) were also found to correlate to the fraction of tumor, connective, fat or glandular tissue by Pearson correlation analysis. Tissue concentrations of ,-glucose correlated to proliferation index (MIB-1) with a negative correlation factor (,0.45, p,=,0.015), consistent with increased energy demand in proliferating tumor cells. By analyzing several metabolites simultaneously, either in ratios or by metabolic profiles analyzed by PCA, we found that tissue metabolites correlate to patients' prognoses and health status five years after surgery. This study shows that the diagnostic and prognostic potential in MR metabolite analysis of breast cancer tissue is greater when combining multiple metabolites (MR Metabolomics). Copyright © 2010 John Wiley & Sons, Ltd. [source] Investigation of metabolite changes in the transition from pre-invasive to invasive cervical cancer measured using 1H and 31P magic angle spinning MRS of intact tissueNMR IN BIOMEDICINE, Issue 2 2009Sonali S. De Silva Abstract The aim of this study was to determine the metabolic changes in the transition from pre-invasive to invasive cervical cancer using high-resolution magic angle spinning (HR-MAS) MRS. Biopsy specimens were obtained from women with histologically normal cervix (n,=,5), cervical intraepithelial neoplasia (CIN; mild, n,=,5; moderate/severe, n,=,40), and invasive cancer (n,=,23). 1H HR-MAS MRS data were acquired using a Bruker Avance 11.74,T spectrometer (Carr,Purcell,Meiboom,Gill sequence; TR,=,4.8,s; TE,=,135,ms; 512 scans; 41,min acquisition). 31P HR-MAS spectra were obtained from the normal subjects and cancer patients only (as acetic acid applied before tissue sampling in patients with CIN impaired spectral quality) using a 1H-decoupled pulse-acquire sequence (TR,=,2.82,s; 2048 scans; 96,min acquisition). Peak assignments were based on values reported in the literature. Peak areas were measured using the AMARES algorithm. Estimated metabolite concentrations were compared between patient diagnostic categories and tissue histology using independent samples t tests. Comparisons based on patient category at diagnosis showed significantly higher estimated concentrations of choline (P,=,0.0001) and phosphocholine (P,=,0.002) in tissue from patients with cancer than from patients with high-grade dyskaryosis, but no differences between non-cancer groups. Division by histology of the sample also showed increases in choline (P,=,0.002) and phosphocholine (P,=,0.002) in cancer compared with high-grade CIN tissue. Phosphoethanolamine was increased in cancer compared with normal tissue (P,=,0.0001). Estimated concentrations of alanine (P,=,0.01) and creatine (P,=,0.008) were significantly reduced in normal tissue from cancer patients compared with normal tissue from non-cancer patients. The estimated concentration of choline was significantly increased in CIN tissue from cancer patients compared with CIN tissue from non-cancer patients (P,=,0.0001). Estimated concentrations of choline-containing metabolites increased from pre-invasive to invasive cervical cancer. Concurrent metabolite depletion occurs in normal tissue adjacent to cancer tissue. Copyright © 2008 John Wiley & Sons, Ltd. [source] An investigation of human brain tumour lipids by high-resolution magic angle spinning 1H MRS and histological analysisNMR IN BIOMEDICINE, Issue 7 2008Kirstie S. Opstad Abstract NMR-visible lipid signals detected in vivo by 1H MRS are associated with tumour aggression and believed to arise from cytoplasmic lipid droplets. High-resolution magic angle spinning (HRMAS) 1H MRS and Nile Red staining were performed on human brain tumour biopsy specimens to investigate how NMR-visible lipid signals relate to viable cells and levels of necrosis across different grades of glioma. Presaturation spectra were acquired from 24 adult human astrocytoma biopsy samples of grades II (8), III (2) and IV (14) using HRMAS 1H MRS and quantified using LCModel to determine lipid concentrations. Each biopsy sample was then refrozen, cryostat sectioned, and stained with Nile Red, to determine the number of lipid droplets and droplet size distribution, and with Haematoxylin and Eosin, to determine cell density and percentage necrosis. A strong correlation (R,=,0.92, P,<,0.0001) was found between the number of Nile Red-stained droplets and the ,1.3,ppm lipid proton concentration by 1H MRS. Droplet sizes ranged from 1 to 10,µm in diameter, and the size distribution was constant independent of tumour grade. In the non-necrotic biopsy samples, the number of lipid droplets correlated with cell density, whereas in the necrotic samples, there were greater numbers of droplets that showed a positive correlation with percentage necrosis. The correlation between 1H MRS lipid signals and number of Nile Red-stained droplets, and the presence of lipid droplets in the non-necrotic biopsy specimens provide good evidence that the in vivo NMR-visible lipid signals are cytoplasmic in origin and that formation of lipid droplets precedes necrosis. Copyright © 2008 John Wiley & Sons, Ltd. [source] Preinvasive and invasive cervical cancer: an ex vivo proton magic angle spinning magnetic resonance spectroscopy studyNMR IN BIOMEDICINE, Issue 3 2004Marrita M. Mahon Abstract The aim of this study was to obtain 1H MR spectra using magic angle spinning (MAS) techniques from punch biopsies (<20,mg) of preinvasive and invasive cervical disease and to correlate the spectral profiles with sample classification on the basis of histopathology. Tissue samples were obtained at colposcopic examination, during local treatment of cervical intraepithelial neoplasia (CIN) or at hysterectomy. 1H MAS MRS was performed at 25°C while spinning the sample at 4.5,kHz. After measurement, the tissue was immersed in formalin and the pathology determined. Histological examination after 1H MAS MRS defined 27 samples with squamous cell carcinoma (SCC), 12 with CIN and 39 with only normal tissue. The standardized integrals of the lipid, choline and creatine regions of the spectra were significantly higher in SCC than in normal or CIN tissue. There was no obvious difference in the standardized integral of the region 4.15,3.5,ppm. The acyl fatty acid side-chain length was longer or less unsaturated in SCC than in normal tissue. Normal tissue from patients with SCC showed significantly higher triglycerides than normal tissue from patients with benign uterine disease but significantly lower triglycerides than SCC tissue. 1H MAS MRS of the uterine cervix ex vivo may be used to differentiate non-invasive from invasive cervical lesions, increase interpretation of in vivo MRS and provide insights into tumor biology. Copyright © 2004 John Wiley & Sons, Ltd. [source] High-resolution magic angle spinning MRS of breast cancer tissueNMR IN BIOMEDICINE, Issue 5 2002Beathe Sitter Abstract High-resolution magic angle spinning (HR MAS) may develop into a new diagnostic tool for studying intact tissue samples, and several types of cancer have been investigated with promising results. In this study HR MAS spectra of breast cancer tissue from 10 patients have been compared to conventional high-resolution spectra of perchloric acid extracts of the same tissue type. The HR MAS spectra show resolution comparable to spectra of extracts, and two-dimensional techniques lead to identification of a majority of the constituents. More than 30 different metabolites have been detected and assigned. To our knowledge this is the most detailed assignment of biochemical components in intact human breast tissue. The spectra of intact breast cancer tissue differ from perchloric acid extracts by the presence of lipids and fewer signals in the low field region. HR MAS analysis of intact breast tissue specimens is a rapid method, providing spectra with resolution where relative quantification of the majority of the detected metabolites is possible. Copyright © 2002 John Wiley & Sons, Ltd. [source] Solid state 19F NMR study of crystal transformation in PVDF and its nanocompositesPOLYMER ENGINEERING & SCIENCE, Issue 12 2006Pramoda K. Pallathadka The polymorphism of poly(vinylidene fluoride) (PVDF) and its nanocomposites was studied by means of solid state nuclear magnetic resonance spectroscopy. 13C cross polarization magic angle spinning (13C CP MAS) NMR spectra were recorded using simultaneous high-power decoupling on both the proton and fluorine channels. Both 1H , 13C and 19F , 13C CP experiments were conducted, giving identical results apart from intensity variations due to the CP efficiency. Two main resonances for the CF2 and the CH2 groups were observed for both neat PVDF (PVDF-C0) and the nanocomposite containing 2 wt% clay (PVDF-C2) samples. 19F CP MAS spectra were obtained from long proton spin-lock experiments with a shorter contact time. The results showed two strong resonances at ,84 and ,98 ppm with equal intensities, representing the ,-form crystalline structure of PVDF. It was shown that the clay induces the crystallization of PVDF in ,-form. Our earlier investigations using thermal analysis and X-ray scattering methods also showed crystal transformation of PVDF in its clay nanocomposites. POLYM. ENG. SCI. 46:1684,1690, 2006. © 2006 Society of Plastics Engineers [source] | |||||||||||||||||||